Process for producing carbon dioxide and hydrogen from carbon monoxide and steam using mixed oxides of copper,zinc and chromium as catalyst and process for producing said catalyst



May 26, 1970 G. w. BRIDGER ErAL 3,514,261

PROCESS FOR PRODUCING CARBON DIOXIDE AND HYDROGEN FROM CARBON MONOXIDE AND STEAM USING MIXED OXIDES OF COPPER, ZINC AND CHROMIUM AS CATALYST AND PROCESS FOR PRODUCING SAID CATALYST Original Filed June 5, 1963 United States Patent O U.S. Cl. 23-213 Claims ABSTRACT OF THE DISCLOSURE Process of producing carbon dioxide and hydrogen by reacting carbon monoxide with steam in the presence of a catalyst comprising the product Obtained by reducing the mixed oxides of copper, zinc and chromium.

This application is a continuation of Ser. No. 284,860 tiled June 3, 1963, now abandoned.

This invention relates to a process for producing carbon dioxide and hydrogen by reacting carbon monoxide with steam in the presence of a catalyst, and to an improved method for making catalysts for use in this and other processes.

According to the invention there is provided a process of producing carbon dioxide and hydrogen which comprises reacting carbon monoxide with steam in the presence of a catalyst comprising the product of partly reducing the mixed oxides of copper, zinc and chromium.

This process is advantageous over many known processes of reacting carbon monoxide with steam in that it can be carried out at lower temperatures. Temperatures in the range 100 C.-350 C. are suitable, especially in the range 150 C.-300 C., whereas using conventional ferrie oxide-chromium oxide catalyst temperatures of 350 C.w 550 C. are often necessary. The process can be operated however at higher temperatures, for example up to 600 C., if desired.

The process may be carried out at pressures over a wide range, conveniently in the range up to 50 atmospheres. Thus for example it may be carried out at slightly superatmospheric pressure in decreasing the carbon monoxide content of domestic heating gas and also at higher pressures for example 10 to 15 atmospheres as in the carbon monoxide-steam reaction in the industrial production of hydrogen.

The process may be carried out at space velocities over a wide range. For example at 250 C. it may be carried out at useful conversions at space velocities of up to 100,000, for example 62,500 hrrl. At lower space velocities, for example up to 20,000 hrs-1, for example 2,800 lin-1, the reaction proceeds substantially to equilibrium at convenient temperatures in the range defined above. Thus the process is valuable for further decreasing the carbon monoxide content of a gas mixture which has already been subject to a conventional water-gas shift catalyst at a higher temperature.

The ratio of steam to carbon monoxide in the inlet gas to the process of the invention depends on the extent of reaction required and on the concentration of the product gases hydrogen and carbon dioxide already present. In treating industrial gases containing carbon monoxide and also one or more of those product gases it is convenient to use an excess of steam in order to increase the extent 3,514,261 Patented May 26, 1970 lCC of the desired reaction. Owing however to the fact that at equilibrium the reaction mixture contains more CO2 and H2 the lower the temperature, the excess of steam required for a given conversion in the process of the invention is less than in older processes at higher temperatures. Likewise using the process of the invention it is possible to attain very low carbon monoxide contents with convenient proportions of steam in the inlet gas.

The inlet gas mixture should preferably be substantially sulphur-free, that is contain sulphur or sulphur compounds to the extent of less than about l parts per million calcue lated as sulphur. It is preferred to have present less than 5 parts per million and more preferably less than 1 part per million. Inlet gas mixtures of such low sulphur contents are produced readily by modern desulphurisation techniques, for example as described in U.K. Patent specification No. 902,148. Very suitable inlet gas mixtures for treatment -by the process of the invention are those produced by the catalysed reaction of steam with desulphurised hydrocarbons. The above sulphur contents are by weight.

The catalyst for the reaction of carbon oxides with hydrogen contains copper, zinc and chromium preferably in a ratio falling within the area substantially defined by perimeter C passing through the following points ou the triangular phase diagram:

Cu Zn Cr Cu Zn Cr so s 2 60 15 25 45 30 90 6 4 The above perimeters are illustrated in the triangular phase diagram shown in the accompanying drawing.

In the diagram the compositions represented are atomic percentages of the total content of copper, zinc and chr0- mium. Where herein reference is made to a percentage copper, zinc or chromium content such a content is a percentage by atoms of the total copper, zinc and chromium. The preferred catalysts thus have a zinc to chromium ratio in the range 1.5 :1 to 4:1 and a copper content in the range 25 %90%. The copper content of such catalysts is more preferably in the range %-85%, especially %-75%. Thus as examples of valuable catalysts for use in the process of the invention there may be mentioned those consisting of the product of reducing the mixed oxides of copper, zinc and chromium in the atomic ratio 30:60:10, 40:40:20, 80:l5:5 and 72:21:7 in increasing order of preference: catalysts having the ratio :30:10 and 75:l8:7 are similar to the 72:21:7 catalyst.

The catalysts may contain support materials, diluents or binding materials, of types 'well known in catalystmaking. These however do not appear to be essential, very satisfactory results being obtained without them. We have also found an improved method for making such catalysts: accordingly the invention profvides a method of producing a catalyst which comprises coprecipitating from solution copper, zinc and chromium as one or more compounds readily convertible to oxides, under such conditions that at the end of the co-precipita- 3 tion stage at most a minor part of the precipitated copper compound has decomposed.

The nature of the decomposition of the copper compound is illustrated by the following description. When a solution of the mixed nitrates of copper, zinc and chromium is added to a solution of sodium carbonate a precipitate is formed which initially is occulent and of a royal blue colour. The precipitate rapidly changes to the pale bluish or greenish condition which is characteristic of the above-mentioned compound, then to a khaki colour which may darken further. The change to the khaki colour and thence to darker colours is the result of decomposition which is to be avoided in the process of the invention. It is believed that copper oxide is one of the products of this decomposition and that it is especially important to avoid the formation of copper oxide during the co-precipitation stage.

The co-precipitation is preferably carried out in the presence of an excess of the acid radical of the compound readily convertible to an oxide. Thus if a batchwise method is employed the solution of the copper, zinc and chromium is preferably added to the solution of that acid radical.

Conditions tending to decrease decomposition of the copper compound appear to include the following:

(a) low temperature for example room temperature; and

(b) short time of contact of the copper compound with alkaline solutions especially at pH values above about 9.5.

The invention includes methods embodying either of these conditions but it is preferred to use condition (b) while keeping the temperature relatively high, for example, at between 80 C. and boiling point.

Conditions (b), the short time of contact of the copper compound with alkaline solutions is of especial importance when the compound is a salt of a Iweak acid, for example a hydroxide or carbonate, and is formed by adding the copper salt, without or with the zinc and/or chromium salts to an alkali metal hydroxide or carbonate. The short times of contact with the alkaline solution may be achieved for example by adding the copper salt, without or with the zinc and/ or chromium salt, to a vessel and at the same time adding the alkaline solution at such a rate that the alkali concentration is continuously and rapidly reduced to a low level, corresponding to a pH less than 9.5 preferably less than about 8 for example between 7.5 and 8.0. (The pH values quoted here and elsewhere in this specification are measured at room temperature.) As an alternative the two solutions may be mixed at a owing junction, the relative rates of ow being adjusted as for simultaneous addition to a vessel.

By making the catalyst by the method of the invention it is found possible to increase the proportion of copper to zinc and chromium in the catalyst in such a 'way that the activity of the catalyst, for example in the carbon monoxide-steam reaction and in the methanol synthesis reaction, is increased. When the attempt is made to make catalysts of high copper proportion that is in which the atomic ratio of copper to zinc-l-chromium is at least 1:1, for example containing 60% of copper by atom, without taking precautions to prevent the abovementioned decomposition of the copper compound the resulting catalysts are somewhat inhomogeneous and are 1o more active than catalysts of a considerably lower :opper proportion. The method of the feature of the Invention may also be used to make a catalyst of lower :opper proportion, for example 30% by atoms of the otal copper-i-zinc-i-chromium content.

The Water-insoluble compound readily convertible to )xide may be for example a hydroxide, carbonate or )xalate or a compound or mixture of two or more of hese, for example a basic carbonate.

The solution forming the precipitate by reaction with he copper, zinc and chromium salts is preferably of an alkali metal compound. Ammonium compounds can be used but are less preferably. The acid radical of this solution may be for example hydroxide, carbonate, bicarbonate or oxalate or a mixture thereof. Conveniently it is carbonate; the precipitate is then a mixture of carbonates, basic carbonates and hydroxides. Conveniently sodium or potassium carbonates are used.

After the co-precipitation stage the precipitate should be to la large extent freed of electrolytes, for example by washing. Suitably the electrolyte content, calculated as sodium oxide equivalent, is less than 1.0%, especially less than 0.1% by weight of the dry solids present. (By dry solids is meant solids stable at 900 C.) The Iemoval of the electrolytes is made easier if the precipitates and mother liquor are heated to a temperature higher than the precipitation temperature, before being separated. After this heating stage but before separation a final adjustment of pH may be made if desired. Alternatively or additionally the separated precipitate may be heated with one or more changes of washing water. These wet heating stages should be carried out with care otherwise the activity of the catalyst may be decreased to some extent.

The copper, zinc 4and chromium salts are preferably acetates or nitrates, especially nitrates: halides and sulphates should preferably not be present at the co-precipitation stage. The copper salt is preferably cupric.

After being washed the precipitate is dried, conveniently at such a temperature for example C.-150 C. that not more than half the total copper compound present is converted to copper oxide. The dried material is calcined at for example 200 C.-300 C. to convert it at least partly to the mixed oxides.

The calcined material may be ground finely for use in a fluid-bed reaction or may be formed into pieces by for example pelleting under pressure using graphite as lubricant. It may also be granulated or extruded and binding agents may also be added.

Before the oxide mixture can show its full activity as a catalyst it should be partly reduced. This may be conveniently effected by passing a reducing gas for example hydrogen or carbon monoxide, preferably diluted with an inert gas such as nitrogen or steam, at atmospheric pressure over the oxide mixture at temperature preferably in the range C.-250 C. When the inlet gases of the process which the catalyst is to catalyse have reducing properties the reduction of the oxide mixture may be effected by these gases preferably suitably diluted in the plant in which the process is to be carried out.

The catalysts made by the method of the invention are highly valuable for the reaction of carbon monoxide with steam., for the synthesis of oxygenated hydrocarbons especially methanol from carbon oxides and hydrogen, especially as described in U.S. application Ser. No. 284,861, led on even date herewith and issued as U.S. Pat. 3,326,956 on J une 20, 1967 in the name of Phineas Davies and Frederick Forster Snowdon, and for organic hydrogenation and dehydrogenation reactions at temperatures up to about 300 C.

The invention is illustrated by the following examples.

EXAMPLE 1 A catalyst consisting of the reduction product of the mixed oxides of copper, zinc and chromium in the ratio 60:30:10 by atoms was made as follows:

A solution of 9.084 kg. of copper nitrate 5.592 kg. of zinc nitrate Zn(NO3)2-6H2O and 2.508 kg. of chromium nitrate Cr(NO3)3-9IH2O dissolved in 100 litres of water was heated to 90 C. and added over 2 minutes with stirring to a solution of 7.674 kg. of sodium carbonate Na2CO3 in 150 litres of water also at 90 C. The pH of the nal mixture measured on a sample at room temperature was 8.0. The colour of the precipitate was a pale green-blue showing that little if any decomposition had taken place. The mixture was stirred for 15 minutes at 90 C., during which no change in colour took place. It was then iiltered and washed by passing cold Water through the residue until the sodium content for 12 hours, with similar results, and the temperature was decreased back to 180 C. No decrease in catalyst activity was observed as the result of the operation at 250 C.; and the activity remained constant during a further 1100 hours at 180 C.

of the residue as shown by gravirnetric analysis after drying at 900 C. was 0.05% by weight as NazO. The residue EXAMPLE 4 Was then dried in all' at 105 C., 'during treatment A peueted mixed oxide composition was made as deno change in colour took place, then calcined in air at Scribedin Examplegbut with the composition 265 C. for 4 hours. The resulting product, which has l0 hereinbefore been referred to as the mixed oxides, was a Cu3-8zn59-7cr95 dark brown Solid- It Was Peueed undef PNSSUW 'i0 PTO and with a coprecipitation mixing time of 30 m-inutes. It 011C@ 3716" by G" Cylindrical Pellets, and SUbeCted T0 a was reduced using hydrogen diluted with nitrogen at 160 reduction Stage J'USll before use, by Passing Over it a C.220 C. There was passed over the resulting catalyst a mixture of hydrogen and nitrogen at atmospheric pressure 15 gas mixture consisting of 6.85% carbon monoxide, 7.65% until no further heat of reaction could be detected: the carbon dioxide, 55% Ihydmggn, 50% Steam and 0,65% final temperature during reduction was 220 C.250 C. methane (percentages by volume) at a temperature The use in methanol synthesis of the above catalyst and of 220 C. (inlet) and 280 C. (exit), a pressure of e catalyst having the composition copper 75rzinc. of 180 psig. and o space veloeity of 4,200 hour-1. schfommm 7 made 111 the Same Wy but With aPPfOPf- 20 The exit gas contained only 0.25% of carbon monoxide. 91 adjustl'l'll'lt Of the quantities Of the Starting materials, In the catalyst used in this example the Sodium content is described in the abovementioned US. at: 3,326,956 was higher, corresponding to 0.3% of Nazo in the dried issued 011 the Copendmg Davies et alaPllifaloll Sel' NG- but uncalcined precipitate, that is, 0.4% on the mixed 2843361- oxides as dried at 900 C.

EXAMPLE 2 25 What is claimed is:

1. A process for producing carbon dioxide and hydro- In a small-scale test of the catalyst of Example 1 a 2.5 g. gen, which comprises reacting carbon monoxide with sample of the pelleted mixed oxides was crushed to pass Steam at a temperature of labout 100 C t0 about 600 C, 1 7-10 BSS- (British Standard Sieve) mesh, then rein the substantial absence of sulphur and in the presence duced as described ilfhldy- Then a mixture 0f 25% cal 30 of a catalyst comprising, as the essential active catalytic 00H IIIOIIOXC, 25% hydrlgen and 50% Steam (Percentmaterial, the product obtained by reducing with hydroages by Volume) Was Passed over the Catalyst at gen or carbon monoxide the mixed oxides of copper, zinc substantially atmospheric pressure, a space velocity of and chromium, said catalyst containing copper, Zinc, and 62,500 holllwl and temperature in the Tango 150 C.250 chromium in a ratio falling within the area defined by the C. The table shows the carbon monoxide contents of the 35 following atomic percentage points on a triangular phase dry inlet gas and dry heated gas, in comparison with diagram: results obtained (a) using a copper-zinc-chromium catalyst made without precautions to avoid decomposition Cu Zn Cr of the copper precipitate and (b) using a conventional 95 4 1 iron oxide-chromium oxide catalyst. (In making catalyst 40 5% nl] (a) it was observed that the precipitate was of a khaki 20 30 50 colour at the end of the co-precipitation stage.) 5 5 Catalyst CusZnanCrm (by the method of CroZnruCriu (Without precautions) the invention) (a) Fe20i-Cr2O3 (conventional) (b) Temperature 150 200 250 150 200 250 35o 400 450 Inlet CO percent by vol.-- 50 50 50 50 50 50 50 50 Exit C0, percent by vol--. 39.2 26. c 1s. a 45. e 35. 2 2s. 9 4o. 7 a3. a 26. 7 Exit CO2, percent by v01 7. 2 15. 6 21.1 3. 0 9. 9 14. 1 6. 2 11. 1 15. 5

Percent conversion 15. 5 37. 0 53. 6 6.1 21. 9 32. 8 13. 2 25. 0 l 36. 8

A catalyst having the compositori 75 CuzlS Zn:7 Cr the mixed oxides being produced by coprecipitating copmade by a method similar to that of Example l, but with per, zinc, and chromium, by mixing an excess of an alkali appropriate adjustment of the quantities of the starting metal compound selected from the group consisting of materials, was tested in the same way. The percentage hydroxides, carbonates, bicarbonates, oxalates, and mixconversions were: tures thereof with a solution of copper, zinc, and chro- Percent mium compounds selected from the group consisting of 150 C 15 nitrates and acetates, the pH of the reaction mixture at 200 C. 38 60 the end of the coprecipitation Ibeing alkaline and below 250 C. 60 9.5, whereby the formation of any substantial amount of copper oxide as evidenced by the obtention of a khaki EXAMPLE 3 color during the coprecipitation step is prevented and then calcining the coprecipitated product to form said A sample of mixed oxides produced as described in mixed oxides, Example 1 was charged to a pilot scale Converter (VOlU'mc 2. A process according to claim 1 wherein the reaction 31/2 litres) and at 160 C.-220 C. reduced using hydrotemperature is in the range 150 C.300" C. and the cogen diluted with nitrogen. A gas mixture containing 0.25 precipitation is carried out at a temperature between carbon monoxide, 12.5% carbon dioxide, 35% hydrogen, C. and the boiling point of the solution. 50% steam and fractional percentages of methane and 70 3. A process according to claim 1 wherein the sulphur inert gases (percentages by volume) Was passed over the content of the inlet gas mixture is less than 5 parts per catalyst at a temperature of C., a space velocity of million by weight. 2,800 hourr, and a pressure of 180 p.s.i.g. The carbon 4. A process according to claim 3 wherein the sulphur monoxide content of the exit gas was found to be only content of the inlet gas mixture is less than 1 part per 75 million by weight.

0.06%. The same process was then operated at 250 C.

5. A process according to claim 1 wherein the pH of the reaction mixture at the end of the coprecipitation is below 8.

6. A process according to claim |1 wherein the precipitate is Washed to decrease its electrolyte content calculated as sodium oxide equivalent to less than 1.0% by weight of the dry solids present.

7. A process according to claim 6 wherein the precipitate is Washed to decrease its electrolyte content calculated as sodium oxide equivalent to less than 0.1% by weight of the dry solids present.

y8. A process as claimed in claim 1 wherein said catalyst contains copper, zinc, and chromium in a ratio falling within the area deined by the following atomic percentage points on a tri-angular phase diagram:

Cu Zn Cr 9. A process for producing a catalyst for the reaction of carbon monoxide with steam at a temperature of about 100 C. to about 600 C., in the substantial absence of sulphur, to produce carbon dioxide and hydrogen, said process comprising: (a) coprecipitating copper, zinc, and chromium in a ratio of copper, zinc, and chromium falling within the area defined by the following atomic peroentage points on a triangular phase diagram:

Cu Zn Cr by mixing an excess of an alkah metal compound selected from the group consisting of hydroxides, carbonates, bicarbonates, oxalates, and mixtures thereof, with a solution consisting essentially of copper, zinc and chromium compounds selected from the nitrates and acetates of said metals, the pH of the reaction mixture at the end of the coprecipitation being alkaline and below 9.5, whereby the formation of substantial amounts of copper oxide as evidenced by the obtention of a khaki color during the coprecipitation step is prevented, (b) calcining the resulting precipitate to obtain said mixed oxides and then (c) reducing the mixed oxides by contacting the same with hydrogen or carbon monoxide to produce said catalyst.

10. The process as claimed in claim 9 wherein said catalyst contains copper, zinc, and chromium in a ratio falling within the area defined by the following atomic percentage points on a triangular phase diagram:

Cu Zn Cr 11. The product produced by the process of claim 9.

\12. A process according to claim 1 wherein the mixed oxides have an atomic ratio of copper to zinc plus chromium of Iat least 1: 1.

References Cited UNITED STATES PATENTS 1,797,426 3/ 193 1 Larson 23--213 1,809,978 6/ 193 1 Larson 23-213 3,074,783 1/ 1963 Paull 23-210 XR 1,746,781 2/ 1930 Lazier 252--468 1,959,3 13 5/ 1934 Vail 252-468 X 2,697,730 12/ 1954 Mecorney et al. 252-468 X FOREIGN PATENTS 636,800 5/ 1950 Great Britain.

EDWARD STERN, Primary Examiner U.S. Cl. X.R. 252-468 

